KR100528046B1 - Fabrication method for ultrafine cermet alloys with a homogeneous solid solution grain structure - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing ultrafine grained cermets, and more particularly, to a process for producing TiC-based cermets having very fine composite carbide grains in the form of a solid solution having no core-rim structure inside the carbide grains.

It is an object of the present invention to provide a method for producing a TiC-based cermet that has no core-rim structure, has a uniform microstructure in terms of components, and has grains of submicron size. The object of the present invention is a nano-composite powder in which Ti-TM (TM = transition metal) composite carbide and Ni-Co metal phase obtained by mechanochemical synthesis (high energy ball milling) coexist, (Ti, TM) C- (Co , Ni) can be achieved by sintering in a general manner.

Description

Fabrication method for ultrafine cermet alloys with a homogeneous solid solution grain structure

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing ultrafine cermet, in particular titanium carbide having very fine composite carbide grains in the form of a solid solution having no core-rim structure inside the carbide grains. It relates to a method for producing a system cermet.

In general, TiC-based cermets are widely used as cutting tool materials for finishing processing of steel and cast iron due to their high hardness and high wear resistance.

TiC-based cermet sintered body is a composite carbide of (Ti, TM) C or (Ti, TM) (C, N) surrounding the core with a core (core) containing TiC or TiCN as a main component inside the carbide grains It is well known to have a unique dual structured microstructure called core-rim divided into regions of constituents (rims) (see FIG. 8; Hans-Olof Andr n, "Microstructures of cemented carbides," Materials and Design, 22, 491-498 (2002)). In addition, the core-rim structure is a result of a grain growth process in which a transition metal (TM) component is dissolved in liquid Ni during liquid sintering and re-precipitates around TiC or TiCN particles in the form of a composite carbide around TiC or TiCN particles. T. Yamamoto, A. Jaroenworaluck, Y. Ikuhara and T. Sakuma, "Nanoprobe analysis of core-rim structure of carbides in TiC-20 wt% Mo ₂ C-20 wt% Ni cermet," Journal of Materials Research , 14, (1999) 4129-4131), or thermodynamically stable equilibrium structures and are known to be formed for kinematic reasons (J.-H. Shim, C.-S. Oh and DN Lee, "A thermodynamic evaluation of the Ti-Mo-C system, "Metallurgical and Materials Transactions B, 27B, (1996) 955-996).

The TiC-based cermet having the core-rim structure does not exhibit the properties of uniform composite carbides allowed by the composition, but exhibits physical properties derived from the carbide grains of the dual structure, and has the disadvantage that the physical properties of the sintered body may be degraded. have. Therefore, the cermet having a uniform microstructure in terms of components has a possibility of exhibiting different physical properties from the existing cermet. However, no reports have been made on TiC-based cermet manufacturing methods that overcome the limitations determined kinetically and do not have a core-rim structure.

Meanwhile, in the development of cutting tool materials in recent years, one of the big flows is to greatly increase the hardness and toughness by making the size of carbide grains from several micrometers (μm) to submicrometers. [0003] A method for producing a submicron grain cutting tool material known to date is to sinter carbide powder having a size of 100 nanometers or less manufactured by a gas phase method or a liquid phase method. However, the gas phase method and the liquid phase method are not only inadequate for mass production of carbide nanopowders, but also have a problem that the nanopowders obtained by these methods are easily oxidized when exposed to the atmosphere.

The present invention devised to solve such a problem is an object of the present invention to provide a TiC-based cermet manufacturing method does not have a core-rim structure.

Another object of the present invention is to provide a high hardness TiC based cermet manufacturing method having a uniform microstructure in terms of components and having a grain size of submicron.

This object of the present invention is a general method of nano-composite powder (Ti, TM) C- (Co, Ni) in which the Ti-TM composite carbide and Ni-Co metal phase obtained by mechanochemical synthesis (high energy ball milling) coexist. By sintering (vacuum sintering).

Ultrafine grained cermet manufacturing method having a uniform solid solution particle structure according to the present invention is mixed with titanium (Ti) powder, transition metal (TM) powder, carbon (C) powder, nickel (Ni) powder and cobalt (Co) powder 50 to 90% by weight of TiC, 5 to 30% by weight of TM _x C _y (x and y are integers), 5 to 30% by weight of nickel (Ni) or cobalt (Co) or a mixture of nickel (Ni) and cobalt (Co) Generating a mixed powder composed of%; Injecting the mixed powder into a reaction vessel together with a ball having a predetermined diameter; Milling intensity with respect to the mixed powder is 5 ~ 50 G (G = gravitational acceleration 9.8 m / s ²⁾ in, and a nanocomposite powder by the number of revolutions per minute are performed for the high-energy ball milling of at least 200 rpm, (Ti, TM Generating C- (Ni, Co), and measuring the temperature of the reaction vessel surface using a non-contact infrared thermometer during the high energy ball milling; And forming and sintering the produced nanocomposite powder.

The titanium (Ti) powder, transition metal (TM) powder, carbon (C) powder, nickel (Ni) powder and cobalt (Co) powder have a purity of 95% or more, a particle size of 1 mm or less, and the transition metal ( TM) powder comprises at least one metal from the group consisting of molybdenum (Mo), tungsten (W), niobium (Nb), vananium (V), and chromium (Cr).

The material of the reaction vessel and the ball is any one of tool steel, stainless steel, cemented carbide, silicon nitride, alumina or zirconia.

The diameter of the ball is 5 to 30mm, the ratio of the mixed powder and the ball to be added to the reaction vessel is 1: 1 to 1: 100 by weight ratio.

Measuring the temperature of the surface of the reaction vessel using a non-contact infrared thermometer during the high energy ball milling, if the rapid rise in temperature of the surface of the reaction vessel is measured for 1 to 20 hours from that point Continue ball milling.

The high energy ball milling is performed using a shaker mill, a vibration mill, a planetary mill or an attritor mill after filling the reaction vessel with argon (Ar) gas. In addition, the sintering is carried out for 1 to 4 hours at a temperature of 1300 ~ 1500 ℃ in a vacuum or argon atmosphere of 10 ^-2 torr or less.

Such a method for producing an ultrafine grain cermet having a uniform solid solution particle structure according to the present invention will be described in more detail as follows.

First, titanium (Ti) powder having a purity of 95% or more / particle size of 1 mm or less, molybdenum (Mo), tungsten (W), niobium (Nb), and vanadium (95% or more of purity / particle size of 1 mm or less) V), transition metal (TM) powders such as chromium (Cr), carbon (C) powder with a purity of at least 95% / particle size of 1 mm or less, nickel (Ni) powder with a purity of 95% or more / particle size of 1 mm or less, and Cobalt (Co) powder having a purity of 95% or more and a particle size of 1 mm or less is 50 to 90% by weight of TiC, 5 to 30% by weight of TM _x C _y (x and y are integers), nickel (Ni) or cobalt ( Co) or a mixture of nickel (Ni) and cobalt (Co) is mixed to 5 to 30% by weight. Here, x and y are determined according to the type of transition metal (TM), the carbide (TM _x C _y ) of the transition metal (TM) may be one or more.

Next, the mixed powder is put into a reaction jar with a ball having a diameter of 5 to 30 mm. At this time, the ratio of the mixed powder and the ball added to the reaction vessel is in the range of 1: 1 to 1: 100 by weight ratio. Here, the reason for limiting the weight ratio of the mixed powder and the ball to 1: 1 to 1: 100 is that when the weight ratio of the mixed powder and the ball is 1: 1 or less, the amount of impurities mixed by the wear of the ball and the container is required. This is because it increases more than. The reaction vessel and the ball is made of any one of tool steel, stainless steel, cemented carbide, silicon nitride, alumina or zirconia.

Next, after filling argon (Ar) gas in the container, the mixed powder is applied to a shaker mill, a vibratory mill, a planetary mill, or an attritor mill. High energy ball milling is performed with a milling strength of 5 to 50 G (G = gravity acceleration 9.8 m / s ² ) and a revolution per minute of at least 200 rpm. Here, the reason for filling the argon (Ar) in the reaction vessel is to prevent the oxidation of the powder by oxygen in the air during milling. Balls used in high-energy ball milling may be all the same size, or two or more balls may be used together.

During high energy ball milling, the temperature of the reaction vessel surface is measured and recorded using a non-contact infrared thermometer to indirectly observe the reaction occurring in the vessel.

During the milling process a sharp rise in vessel surface temperature as shown in FIG. 1 can be observed. This rapid rise of the surface of the vessel is caused by the heat released when (Ti, TM) C is formed by the reaction of the elemental powders during milling in the reaction vessel.Afterwards, the temperature decreases slowly after the reaction is completed. This is because it slowly exits. Sudden increase in temperature is affected by the weight ratio of the mixed powder and the feed, but is usually observed between 1 and 2 hours after the start of milling. After the exothermic reaction is completed, high energy ball milling is continued for 1 to 20 hours. The reason for continuing milling is to lower the grain size of the formed (Ti, TM) C to about 10 nm.

Next, the powder synthesized by high energy ball milling is recovered and molded, and the molded body is sintered in a vacuum or argon atmosphere of 10 ^-2 torr or less. At this time, the sintering temperature was 1300-1500 degreeC, and the sintering time was 1-4 hours.

The present invention will be described in detail through the following examples.

Example 1

Titanium (Ti) powder with purity 99.7% / particle size 45㎛, Molecular powder (Mo) with purity 99.7% or more / particle size 5㎛, carbon (C) powder with purity over 99% / particle size 5㎛, purity Nickel (Ni) powder of 99.7% or more / particle size 6㎛ was mixed so that the final composition is 60% by weight of TiC, 20% by weight of Mo ₂ C, 20% by weight of nickel (Ni). The mixed powder was put together in a tool steel reaction vessel with a tool steel diameter of 9.5 mm and a weight ratio of 10: 1, and filled with argon gas in a reaction vessel, and high energy ball milling was performed for 20 hours using a shaker mill. The temperature of the reaction vessel surface was measured and recorded using a non-contact infrared thermometer. As shown in FIG. 1, when milling passed about 100 minutes, the surface temperature of the reaction vessel rapidly increased. The milled powder was recovered and molded at a pressure of 20 MPa, and the molded body was sintered for 1 hour at 10 ^-5 torr in a vacuum atmosphere.

2 shows the X-ray diffraction pattern change of the powder with high energy ball milling time. The elements of titanium (Ti), molybdenum (Mo), carbon (C) and nickel (Ni) before milling were changed into a mixed phase of (Ti, Mo) C and nickel (Ni) after milling for 5 hours. When milling was continued, no further phase change was observed, and the height of the diffraction curve was decreased and the width was increased. This means that the (Ti, Mo) C phase is first formed during milling, and the grains are crushed by the mechanical energy of subsequent milling, thereby reducing the size of the grains. The (Ti, Mo) C grain size calculated from the X-ray diffraction pattern after 20 hours milling is about 10 nm.

3 is a scanning electron micrograph of a powder prepared by milling for 20 hours. The powder shape is irregular and takes the form of agglomerated particles having a size of about 1 μm.

4 is a scanning electron microscope microstructure photograph of a TiC-based cermet obtained by sintering the prepared powder. Slightly angled round gray particles in the picture are (Ti, Mo) C grains, and the bright part is Ni matrix (Ni-rich solid solution). In contrast to the microstructure of the TiCN-based cermet prepared by the conventional method as shown in FIG. 8, in the cermet according to the present invention, the core-rim structure did not appear inside the carbide particles, and the size of the carbide particles was also very fine. The average size of the carbide particles measured through image analysis is about 0.5 μm, which is very fine compared to 2 to 5 μm of the carbide particle size of the conventional cermet.

The hardness of the cermet according to the invention was about 92 HRA, and this high hardness value is believed to be due to the fine size of the carbide. In addition, the reason that the cermet prepared according to the present invention does not have a core-rim structure is that the phase formed during the high energy ball milling process is not a composite phase in which TiC and Mo ₂ C are mixed, but a thermodynamically stable solid solution (Ti, Mo) C. This is because there was no nonuniformity in the powder that could form to form the core-rim.

5 is a transmission electron microscope microstructure photograph of a TiC-based cermet prepared according to the present invention. Fine carbide particles of submicron are observed, and it can be seen that there is no tissue nonuniformity inside the carbide particles. It can be seen that the concentrations of Ti and Mo are constant throughout the carbide particles in Table 1 below, which shows the chemical composition of the carbide center and periphery analyzed by X-ray spectroscopy mounted on the transmission electron microscope.

Example 2

Purity 99.7% / Titanium (Ti) powder with a particle size of 45 ㎛, purity 99.9% or more / Tungsten (W) powder with a particle size of 1 ㎛, 99% purity or more / carbon (C) powder with a particle size of 5 ㎛, purity 99.7% Nickel (Ni) powder with a particle size of 6㎛, purity 99.8% or more / Cobalt (Co) powder with a particle size of 10㎛, the final composition is 65% by weight of TiC, 20% by weight WC, 8% by weight Ni, 7% by weight Co Mix to%. The mixed powder was put together in a tool steel reaction vessel in a weight ratio of 8 mm diameter to a cemented carbide 8 mm and 23: 1, and filled with argon gas in a reaction vessel, and high energy ball milling was performed for 5 hours using a planetary mill. The temperature of the reaction vessel surface was measured and recorded using a non-contact infrared thermometer. The milled powder was recovered and molded at a pressure of 20 MPa, and the molded body was sintered for 1 hour at 10 ^-5 torr in a vacuum atmosphere.

6 shows the X-ray diffraction pattern of the powder after high energy ball milling for 5 hours. It was a mixed powder of titanium (Ti), tungsten (W), carbon (C), nickel (Ni) and cobalt (Co) element powders before milling. After 5 hours of milling, (Ti, W) C composite carbides were formed. Nickel (Ni) and cobalt (Co) are believed to form a solid solution with each other. The (Ti, W) C grain size calculated from the X-ray diffraction pattern is about 10 nm.

7 is a scanning electron microscope microstructure photograph of a (Ti, W) C-based cermet obtained by sintering the prepared powder. The slightly gray rounded gray particles in the picture are grains of (Ti, W) C and the bright part is Ni-Co matrix (Ni-Co solid solution). In the cermet according to the present invention, the core-rim structure did not appear inside the carbide particles, and the size of the carbide particles was also very fine. The average size of the carbide particles measured through image analysis is about 0.6 μm, which is very fine compared to 2 to 5 μm of the carbide particle size of the conventional cermet. The hardness of the cermet according to the invention was about 92 HRA, and this high hardness value is believed to be due to the fine size of the carbide.

According to the present invention, crystal grains of about 10 nm obtained by elemental powders of titanium (Ti), transition metal (TM), carbon (C), nickel (Ni) and cobalt (Co) as raw materials and obtained by high energy ball milling By sintering the nanocomposite powder, (Ti, TM) C- (Ni, Co), having a size, it is possible to prepare a cermet alloy of uniform solid solution composite carbide grains having no core-rim structure and having a grain size of submicron. This makes it possible to produce a new microstructured cermet alloy having a high hardness that is difficult to manufacture by a conventional method in a relatively simple process.

1 is a graph showing the temperature change of the reaction vessel surface with milling time during high-energy ball milling.

2 is a graph showing the change of X-ray diffraction pattern with milling time during high energy ball milling of TiC-20 wt% Ni powder.

3 is a scanning electron micrograph of TiC-20 wt% Mo ₂ C-20 wt% Ni powder subjected to high energy ball milling for 20 hours.

Figure 4 is a scanning electron micrograph showing the microstructure of the (Ti, Mo) C-Ni cermet prepared according to the present invention.

5 is a transmission electron micrograph showing the microstructure of the (Ti, Mo) C-Ni cermet prepared according to the present invention.

6 is a graph showing an X-ray diffraction pattern during 5 hours high energy ball milling of TiC-20 wt% WC-8 wt% Ni-7 wt% Co powder.

7 is a scanning electron micrograph showing the microstructure of the (Ti, W) C- (Ni, Co) cermet prepared according to the present invention.

8 is a scanning electron micrograph showing the microstructure of the TiC-TiN-Mo ₂ C-Ni cermet prepared according to the conventional method.

Claims (10)

50 to 90 wt% of TiC, TM _x C _y (x and y are integers) by mixing titanium (Ti) powder, transition metal (TM) powder, carbon (C) powder, nickel (Ni) powder and cobalt (Co) powder ) 5 to 30% by weight, nickel (Ni) or cobalt (Co) or 5 to 30% by weight of a mixture of nickel (Ni) and cobalt (Co) to produce a mixed powder; Injecting the mixed powder into a reaction vessel together with a ball having a predetermined diameter; Milling strength of the mixed powder is 5 ~ 50 G (G = gravitational acceleration 9.8 m / s ² ), and the nano-composite powder, (Ti, TM) by performing a high-energy ball milling at least 200 rpm Generating C- (Ni, Co), and measuring the temperature of the reaction vessel surface using a non-contact infrared thermometer during the high energy ball milling; Molding and sintering the produced nanocomposite powder; Ultrafine grained cermet manufacturing method having a uniform solid solution particle structure comprising a. The method of claim 1, wherein the titanium (Ti) powder, transition metal (TM) powder, carbon (C) powder, nickel (Ni) powder and cobalt (Co) powder has a purity of 95% or more, the particle size of 1mm or less A method for producing an ultrafine grain cermet having a uniform solid solution particle structure. The method of claim 1, wherein the reaction vessel and the material of the ball are any one of tool steel, stainless steel, cemented carbide, silicon nitride, alumina, or zirconia. The method of claim 1, wherein the transition metal (TM) powder is at least one metal from the group consisting of molybdenum (Mo), tungsten (W), niobium (Nb), vananium (V), chromium (Cr). Ultrafine grained cermet manufacturing method having a uniform solid solution particle structure comprising a. The method of claim 1, wherein the diameter of the ball is 5 to 30mm, the ratio of the mixed powder and the ball to be added to the reaction vessel has a uniform solid solution particle structure, characterized in that the range of 1: 1 to 1: 100 by weight ratio. Ultrafine Grain Cermet Manufacturing Method. delete The ultrafine crystal grain having a uniform solid solution particle structure according to claim 1, wherein if a rapid temperature rise of the surface of the reaction vessel is measured by the non-contact infrared thermometer, high energy ball milling is continued for 1 to 20 hours. Method of making a mat. The ultrafine grain having a uniform solid solution particle structure according to any one of claims 1 to 6, wherein the high energy ball milling is performed using a shaker mill, a vibration mill, a planetary mill, or an attritor mill. Cermet manufacturing method. The ultrafine grain cermet manufacturing method according to any one of claims 1 to 6, wherein the reaction vessel is filled with argon gas and then high energy ball milling is performed. The ultrafine crystal cermet according to claim 1, wherein the sintering is performed for 1 to 4 hours at a temperature of 1300 to 1500 ° C in a vacuum or argon atmosphere of 10 ^-2 torr or less. Manufacturing method.